JP5404514B2 - Epoxy resin production method, epoxy resin, and curable resin composition - Google Patents

Description

  The present invention relates to a method for producing an epoxy resin having a specific structure, and an epoxy resin obtained thereby.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists.
In the field of optoelectronics, especially in recent years, with advanced information technology, in order to smoothly transmit and process huge amounts of information, technology that utilizes optical signals has been developed instead of conventional signal transmission using electrical wiring. In the meantime, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired.

In particular, epoxy resin anhydrides are often used in fields requiring optical properties, such as LED products. Conventionally, as an epoxy resin used as a sealing material for an optical semiconductor element such as an LED product, a glycidyl ether type typified by a bisphenol A type epoxy resin excellent in balance of heat resistance, transparency and mechanical properties. The epoxy resin composition has been widely used.
However, as the light emission wavelength of LED products has been shortened (mainly blue light emission of 480 nm or less), the sealing material is colored on the LED chip under the influence of short wavelength light, and finally the LED product. It has been pointed out that the illuminance will decrease.
Therefore, an alicyclic epoxy resin represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate is more transparent than a glycidyl ether type epoxy resin composition having an aromatic ring. Since it is excellent in terms, it has been actively studied as an LED sealing material. (Patent Documents 1 and 2)

JP-A-9-213997 Japanese Patent No. 3618238 JP 2006-316034 A

  In addition, bifunctional epoxy resins have been developed as epoxy resins that can be adapted to such fields. Such an epoxy resin is difficult to manufacture unless it is conventionally produced by a special method. For example, it has been reported that by adding an alkylaminophosphonium compound or the like, the reaction proceeds selectively to produce a bifunctional epoxy compound. However, special alkylaminophosphonium compounds are difficult to obtain, and a simpler production method is required (Patent Document 3).

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
A method for producing an epoxy resin having a (meth) allyl group and an epoxy group,
(A) A step of obtaining an aqueous solution containing tungstic acids and / or salts thereof, phosphoric acids and / or salts thereof (B) A step of adding a quaternary ammonium salt (C) A step of adding an aqueous hydrogen peroxide solution ( Either before or after each step of A) to (C),
(D) A method for producing an epoxy resin, characterized by performing epoxidation through a step of adding a compound having a (meth) allyl group and a cyclohexenyl group,
(2)
A method for producing an epoxy resin, wherein the tungstic acid and / or its salt is one selected from tungstic acid, tungstophosphoric acid and / or its salt,
(3)
The method for producing an epoxy resin according to (1) or (2) above, wherein the epoxy resin is brought into contact with at least one of a composite metal salt, activated carbon, layered clay mineral, metal oxide, and phenol resin polymer,
(4)
An epoxy resin having a (meth) allyl group and an epoxy group having one or more selected from trimethylolalkane, pentaerythritol, dipentaerythritol, ditrimethylolalkane as a skeleton,
(5)
A curable resin composition comprising at least one epoxy resin according to item (4) obtained by the method according to any one of items (1) to (3);
(6)
The present invention relates to an epoxy group-containing polymer or oligomer derived from an epoxy resin obtained by the method according to any one of (1) to (3).

  The production method of the present invention is simpler than the conventionally known selective epoxidation method, and according to this production method, a compound that cannot be separated by distillation can be produced, and is excellent in versatility. In addition, the compound obtained by this reaction is extremely useful as an optical material, particularly as an adhesive or sealing material for optical semiconductors (such as LED products).

The present invention relates to a technique for selectively epoxidizing a compound having a (meth) allyl group and a cyclohexenyl group (hereinafter referred to as a bifunctional olefin resin). In the present invention, the (meth) allyl group means an allyl group or a methallyl group.
Hereafter, the manufacturing method of the epoxy resin of this invention is described.
In the production method of the present invention, an epoxidation method using hydrogen peroxide using tungstic acid as a catalyst is adopted.
As a specific method, the reaction is performed in a suspended state of a bifunctional olefin resin, a tungstic acid and / or a salt thereof, and a quaternary ammonium salt, which are raw materials, in an organic solvent, a phosphate, and hydrogen peroxide solution.

The bifunctional olefin resin is not particularly limited as long as it is a compound having a (meth) allyl group and a cyclohexenyl group, and specifically, allyl = cyclohexenecarboxylate or the following (Chemical Formula 2), It is a cyclohexene carboxylic acid ester of a partial allyl ether compound of a polyfunctional alcohol having two or more functions. However, it is not limited to what is shown in the following (Chemical Formula 2). In the present invention, a tri- or higher functional polyhydric alcohol as shown in the following (Chemical Formula 2) and a cyclohexene carboxylic acid ester of a compound having a (meth) allyl group are preferable, and in particular, trimethylolalkane, pentaerythritol, dipentaerythritol, A compound having a ditrimethylolalkane as a skeleton is preferable.
There are various esterification methods. For example, dehydration esterification reaction (reference document Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980)), transesterification reaction (reference patent document JP-A-2006-2006). 052187) and the like.

（式中、複数存在するＲ^１、Ｒ^２はそれぞれ独立して存在し、Ｒ^１は水素原子、メチル基を、Ｒ^２は炭素数１〜６のアルキル基を表す）

(In the formula, a plurality of R ¹ and R ² each independently exist, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms)

In the present invention, in the oxidation reaction of the bifunctional olefin resin using hydrogen peroxide, the reaction is performed through the following steps (A), (B), and (C).
(A) A step of obtaining an aqueous solution having a pH of 6 to 8 containing tungstic acids and / or salts thereof, phosphoric acids and / or salts thereof,
(B) adding a quaternary ammonium salt;
(C) Step of adding aqueous hydrogen peroxide solution In this step, the following steps (D) and (E) may come before and after either step (A) or (B).
(D) A step of adding a compound having a (meth) allyl group and a cyclohexenyl group (E) A step of adding an organic solvent, ie, (Example 1) (D) → (E) → (A) → (B) → ( C)
(Example 2) (E) → (A) → (D) → (B) → (C)
(Example 3) (E) → (A) → (B) → (D) → (C)
(Example 4) (A) → (D) → (E) → (B) → (C)
You can do it in the order. Here, the step (E) may be omitted as necessary. The case where it can be omitted includes, for example, the case where the reaction product substitutes for a solvent.

Tungstic acids and / or salts thereof include tungsten-containing (hetero) polyacids or salts thereof. Here, in the present invention, (hetero) polyacid means polyacid or heteropolyacid. Specific examples of the compound include acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and salts thereof. In the present invention, it is particularly preferable to use two kinds in combination.
Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions.
Specific examples include, but are not limited to, quaternary ammonium ions such as ammonium ions, alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium, potassium and cesium.
Particularly preferably, one or more compounds selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and alkali or alkaline earth metal salts of tungstic acid, 12- Alkali or alkaline earth metal salt of tungstophosphoric acid, alkali or alkaline earth metal salt of 12-tungstoboric acid, alkali or alkaline earth metal salt of 18-tungstophosphoric acid, alkali or alkaline earth metal of 12-tungstosilicate A combination of one or more compounds selected from salts is preferred, and in particular, one or more compounds selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstosilicic acid and alkali or alkaline earth metal salts of tungstic acid, 12 -Tongue The combination of one or more compounds selected from alkali or alkaline earth metal salts of Trinh acid.
The amount used is 1.0 to 20 mmol, preferably 2.0 to 20 mmol, and more preferably 2.5 to 10 mmol, in terms of tungsten element, with respect to 1 mol of olefin (functional group equivalent).

Subsequently, the above-described tungstic acid and / or salt thereof, phosphoric acid and / or salt thereof are combined to produce an aqueous solution.
At this time, the phosphoric acid and / or salt thereof to be used is used as a buffer, and is preferably used in such an amount that the pH in the aqueous solution is adjusted to a range of 5-9, more preferably pH 5. -8, particularly preferably pH 6-8. When the pH is less than 5, it is not preferable because the hydrolysis reaction or polymerization reaction of the epoxy group proceeds, and when the pH is more than 9, the reaction is extremely slow and the reaction time is too long. Absent.
Examples of usable phosphoric acid and / or a salt thereof include phosphoric acid, alkali metal dihydrogen phosphate (alkaline earth metal) salt, dialkali metal hydrogen phosphate (alkaline earth metal) salt, and alkali metal phosphate (alkaline earth). Metal) salt, polyphosphoric acid, alkali metal polyphosphate (alkaline earth metal), tripolyphosphoric acid, alkali metal tripolyphosphate (alkaline earth metal), and the like, but are not limited thereto.

In step A, an aqueous solution of the above-described tungstic acid and phosphoric acid (or phosphate) is prepared, and the amount of water at that time is 2 to 100 times the total amount of tungstic acid used, more preferably 2 to 50. Times, particularly preferably 2 to 30 times.
In step A, an organic solvent may be added. As an organic solvent that can be used,
There is no particular limitation.

As the quaternary ammonium salt in Step B, any quaternary ammonium salt having a total carbon number of 16 or more can be used, and in particular, the alkyl chain is preferably an aliphatic chain.
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (for example, trialkylmethyl whose alkyl group is a mixed system of octyl group and decanyl group) ammonium salt, Examples include hexadecylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to these. Particularly preferred are those having 25 to 100 carbon atoms.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the catalyst in the organic layer becomes poor. When the number of carbon atoms is 25 or less, the hydrophilicity is increased, and the compatibility of the catalyst with the organic layer is similarly deteriorated.

Among these anion species, anions such as halide ions (chloride ions, bromide ions, iodide ions, etc.), nitrate ions, sulfate ions, hydrogen sulfate ions, carboxylate ions (acetate ions, carbonate ions, formate ions), etc. In particular, in the present invention, sulfate ion, methyl sulfate ion, hydrogen sulfate ion, and carboxylate ion are preferable. Most preferred is a carboxylate ion from the viewpoint that hydrolysis of an epoxy group and hydrolysis of an ester bond hardly occur and the target product can be obtained in a high yield.
Even quaternary ammonium salts having counter anions such as sulfate ion, methyl sulfate ion, hydrogen sulfate ion, and carboxylate ion may retain halogen. However, in the present invention, the total halogen content should be 1% or less. Is preferred. When the total halogen content exceeds 1%, a large amount of halogen remains in the product, which is not preferable.
The amount of the quaternary ammonium salt to be used is generally used to ionically bond with tungstic acid ions and move tungstic acid between phases. Therefore, a quaternary ammonium salt usually having a valence of tungstic acid or higher is added.
However, this reaction is characterized by using a trace amount of a quaternary ammonium salt with respect to the valence of tungstic acid, which is different from usual.

The amount of quaternary ammonium salt used is usually less than 1 mole of the valence of tungstic acid (for example, phosphotungstic acids such as phosphotungstic acid and sodium phosphotungstic acid have a valence of 3 and therefore 1 mole of phosphotungstic acid). 3 mol or less, or tungstic acid such as tungstic acid or sodium tungstate, the valence is 2, so 2 mol or less for 1 mol of tungstic acid). Preferably they are 0.01 times mole or more and 0.8 times mole or less, Especially preferably, they are 0.01 times mole or more and 0.5 times mole or less.
In general, the quaternary ammonium salt is used in the same amount or in excess of the tungstic acid to be used. In the present invention, the excess quaternary ammonium salt not only hinders the reaction but also completes the reaction. This causes problems such as poor separation of the organic layer and aqueous layer later, and further remaining in the final product, resulting in poor thermal stability. Conversely, when the amount of the quaternary ammonium salt is too small, the reaction does not proceed at all, or the hydrolysis reaction of the produced epoxy resin proceeds with priority over the target epoxidation reaction rate, which is not preferable.

The hydrogen peroxide in step C is preferably a hydrogen peroxide concentration of 10 to 40% because of its easy handling. When this concentration exceeds 40%, handling becomes difficult and the decomposition reaction of the produced epoxy compound also tends to proceed.
The amount of hydrogen peroxide used is 1.05 to 1.20 mol, more preferably 1.05 to 1.175 mol, based on 1 mol of the cyclohexenyl group of the compound having a (meth) allyl group and a cyclohexenyl group. More preferably, it is 1.06-1.15 mol.
Excess hydrogen peroxide tends to facilitate hydrolysis of the resulting epoxy resin, and excessive hydrogen peroxide is not preferred because it stops the reaction and proceeds with hydrolysis.

  The amount of the organic solvent in the step E is 0.3 to 10, preferably 0.3 to 5, by weight with respect to the compound 1 having a (meth) allyl group and a cyclohexenyl group as the reaction substrate. Preferably it is 0.5-2.5. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of usable organic solvents include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. it can. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used. In the present invention, alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene are preferred.

  Although reaction temperature is not specifically limited, 0-90 degreeC is preferable, More preferably, it is 0-75 degreeC, Especially 15 to 60 degreeC is preferable. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. The preferred range is 1 to 48 hours, more preferably 3 to 36 hours, and still more preferably 4 to 24 hours.

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. As a method for quenching hydrogen peroxide, a reducing agent can be used, and quenching may be performed with a basic compound. In the present invention, it is particularly preferable to carry out both of them. As a preferable treatment method, it is preferable to quench the remaining hydrogen peroxide using a reducing agent after adjusting the pH to 6 to 11 with a basic compound. When the pH is less than 6, the heat generated when reducing excess hydrogen peroxide is large, and the produced epoxy compound is partially hydrolyzed. Moreover, when pH is larger than 11, it may cause hydrolysis of epoxy, and further hydrolysis such as ester bond.

  Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, and ascorbic acid. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
These basic compounds include water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol and isopropyl alcohol. As long as it dissolves in various solvents (such as alcohols such as alcohol), it may be added as a solution of water or an organic solvent (described above) or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

  After hydrogen peroxide quench (or before quenching), the organic and aqueous layers are separated. At this time, when the organic layer and the aqueous layer are not separated, or when no organic solvent is used, the above-mentioned organic solvent is added for operation, and the reaction product is extracted from the aqueous layer. The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio with respect to the raw material polyvalent alkene compound obtained. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.

A quaternary ammonium salt remains in the obtained organic layer. In particular, in the present invention, a quaternary ammonium salt having a large carbon number is used, and most of the quaternary ammonium salt remains in the organic layer and is difficult to remove even by washing with water. Furthermore, since the quaternary ammonium salt serves as a curing accelerator for the epoxy compound and triggers the polymerization, the remaining is not preferable. It also causes coloration during long-term storage. Therefore, impurities (for example, remaining quaternary ammonium salts) can be removed from the obtained organic layer with treatment agents such as ion exchange resins, metal oxides, activated carbon, composite metal salts, viscous minerals, and phenol resin polymers as necessary. And after performing further water washing, filtration, etc. as needed, the target epoxy resin is obtained by distilling a solvent off. In the present invention, purification with these treatment agents is preferred, and treatment with a composite metal salt, activated carbon, layered clay mineral, metal oxide, or phenol resin polymer is particularly preferred. By this production method, the purification step by distillation or the like can be reduced, and the product can be taken out with high yield.
In general, when the production is carried out by this method, both the conversion rate and the selectivity are obtained at 80% or more, further 85% or more, particularly 90% or more, and the yield exceeds 80%.

The composite metal salt is preferably a hydrotalcite-like compound. The hydrotalcite-like compound, a general formula _{^{[M 2+ 1-x MM 3+}} x (OH) 2] a compound represented by _{^{[A n- x / n · mH}} 2 O], and M ²⁺ M ³⁺ is a divalent and trivalent metal ions, a ^n- _{x / ⁿ} denotes the interlayer anions. Specifically, a typical hydrotalcite is a compound represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O.
As a commercial product, the Kyoward series, a product of Kyowa Chemical, is effective. Examples include Kyoword 500, Kyoword 1000, Kyoword 700, Kyoword 600, Kyoword 200, Kyoword 2000, and the like. In the present invention, among the components to be contained, a structure in which magnesium oxide> aluminum oxide and magnesium oxide> silicon dioxide in the quantity ratio of magnesium oxide, aluminum oxide and silicon dioxide is preferable. Specifically, Kyoto word 500, Kyoto word 1000, etc. are preferable.
The amount of the composite metal salt used is preferably 0.05 to 10, more preferably 0.2 to 5, with respect to compound 1 (weight ratio) having a (meth) allyl group and a cyclohexenyl group in the charged molecule. Especially 0.3-3 are preferable.
As activated carbon which can be used, chemical activated carbon is preferable. The chemical activated charcoal is not particularly limited as long as it has been treated with, for example, zinc chloride, phosphoric acid, etc., but the product activated with zinc chloride is particularly preferable because it may introduce chlorine into the product. Phosphoric acid activated charcoal. In addition, activated carbon obtained by a physical method that is made porous with water vapor, air, carbon dioxide, etc., can be used in combination with chemically activated carbon depending on the conditions to be treated. A proportion of more than 50% by weight is preferable.
Examples of the raw material include wood (sawdust, etc.), coal (lignite, peat, coal, etc.), coconut shell, phenol resin, etc. In the present invention, wood is particularly preferred.
Commercially available products include Futamura Chemical, Dazai series (CG, CW, G, QW, S, ACF, etc. series), Ajinomoto Fine Techno Hokuetsu series (SD, BA, F, ZN, Y-180C, H-10CL, H-8CL, G-10F, CL-K, etc.), Nippon Enviro Chemicals Shirataka (C, LGK-400, G series, DO series, Wc, Sx, WHA, etc.), carborafine, etc., PK made by NORIT Series, PKDA series, ELORIT, AZO, DARCO series, HYDRODACO series, PETRODARCO, GAC, series, GCN, C GRAN, ROW, ROY, ROX, RO, RB, R, R.R. EXTRA, SORBNORIT, GF series, CNR, ROZ, RBAA, RBHG, RZN, RGM, SX, SA, D10, VETERAIRIR, PN, ZN, SA-SW, W, GL, SAM, HB PLUS, EUR, USP, CA , CG, GB, CAP SUPER, CGP SUPER, S-51 series, HDB, HDC, HDR, HDW, GRO SAFE, FM-1, PAC series, etc., and Kuraray RP-20, YP-17D, and the like.
The amount of the chemically activated activated carbon used is preferably 0.005 to 10, more preferably, when using a method such as dispersion with respect to the compound 1 (weight ratio) having a (meth) allyl group and a cyclohexenyl group in the charged molecule. Is preferably 0.01 to 4, particularly 0.01 to 0.4. When letting it pass, 0.005-50 is preferable similarly, More preferably, it is 0.05-40, Especially 0.1-30 are preferable.

As the clay mineral, a smectite-based layered clay mineral is preferable, and examples include bentonite, montmorillonite, beidellite, nontronite, saponite, hectorite, and synthetic smectite.
Commercially available products are Kunimine Industries; smecton (synthetic smectite), bentonite (sodium salt type, calcium salt type), Kunipia F (montmorillonite), made by Hojun; Manufactured by Co-op Chemical; the Lucentite series.
The amount of the clay mineral used is preferably 0.005 to 10, more preferably, when using a method such as dispersion with respect to the compound 1 (weight ratio) having a (meth) allyl group and a cyclohexenyl group in the charged molecule. 0.01-4, especially 0.01-0.4 are preferable. When letting it pass, 0.005-50 is preferable similarly, More preferably, it is 0.05-40, Especially 0.1-30 are preferable.

Phenol / formaldehyde resins that can be used are preferably those that do not dissolve in toluene at a concentration of 1% or more, and particularly those that are macroporous powdery to granular.
Commercially available products include Ajinomoto Fine Techno; Hokuetsu HS, Hokuetsu KS, and the like.
The amount of the phenol / formaldehyde resin used is preferably 0.01 to 5 and more preferably 0.05 to 2 with respect to the compound 1 (weight ratio) having a (meth) allyl group and a cyclohexenyl group in the charged molecule. In particular, 0.05 to 1 is preferable.

  These treatment agents may be used individually or in combination, and the treatment may proceed in order. Also, there is no particular designation regarding the processing order.

The epoxy resin thus obtained has, as a main component, a structure in which the cyclohexene structure is selectively epoxidized among the cyclohexene structure and the (meth) allyl group. As other components, there are unreacted substances, partially epoxidized substances, epoxidized (meth) allyl groups, hydrolysates, and these decomposed products and polymers in a proportion of 15% or less in the total weight. It doesn't matter.
Specific examples of the structure include compounds corresponding to the bifunctional olefin resins presented above, and examples thereof include 3,4-epoxycyclohexanecarboxylic acid = 2-propene and the following structures. Not limited to).

（式中、複数存在するＲ^１、Ｒ^２はそれぞれ独立して存在し、Ｒ^１は水素原子、メチル基を、Ｒ^２は炭素数１〜６のアルキル基を表す）

(In the formula, a plurality of R ¹ and R ² each independently exist, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 6 carbon atoms)

  The obtained epoxy resin can be used as various resin raw materials. For example, epoxy acrylate and its derivatives, oxazolidone compounds, cyclic carbonate compounds and the like can be mentioned.

Furthermore, since the obtained epoxy resin has a (meth) allyl group in its structure, it can be polymerized with a polymerization initiator or the like to obtain an epoxy group-containing polymer (or oligomer). A compound having only one allyl group or methallyl group can be a linear polymer (or oligomer), and a compound having two or more (meth) allyl groups can act as a cross-linking agent and extend a chain in three dimensions. This helps to improve mechanical properties such as toughness of the product.
Examples of the polymerization method include those described in JP-A-2007-204642.

  In addition, after reacting the epoxy group with a curing agent as described later, for example, the remaining (meth) allyl group is used as a polyallyl resin, and reacted with maleimide or a thiol compound. It is also possible to obtain a cured product by polymerization. (Reference http://www2.toagosei.co.jp/develop/trend/No1/1metariru.pdf)

Hereinafter, a curable resin composition using the epoxy resin of the present invention (or an epoxy group-containing polymer or oligomer derived from the epoxy resin of the present invention) will be described. Hereafter, the epoxy resin of the present invention means one containing an epoxy group-containing polymer derived from the epoxy resin of the present invention.
The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.

  Other epoxy resins that can be used in combination in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. . Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Epoxy having a glycidyl group and / or an epoxycyclohexane structure Shi resin) include solid or liquid epoxy resins such as, but not limited thereto.

In particular, when the curable resin composition of the present invention is used for optical applications, an alicyclic epoxy resin or an epoxy resin having a siloxane structure (Si-O), such as an epoxy group-containing silicone resin, preferably an epoxy having a silsesquioxane structure Use in combination with a resin is preferred. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These alicyclic epoxy resins include esterification reaction of cyclohexene carboxylic acid with alcohols or esterification reaction of cyclohexene methanol with carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) )), Or Tyschenko reaction of cyclohexene aldehyde (method described in JP 2003-170059 A, JP 2004-262871 A, etc.), and transesterification of cyclohexene carboxylic acid ester (JP A And a compound obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Application Publication No. 2006-052187.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

  Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out the reaction while azeotropic dehydration using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), A method using an organic solvent (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.

  Specific examples of these epoxy resins include ERL-4299 (manufactured by Dow Chemical), Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries) and dicyclopentadiene diepoxide. It is not limited (Reference: Review Epoxy Resin Fundamentals I p76-85). These may be used alone or in combination of two or more.

In particular, in the case of an epoxy resin having a siloxane structure (Si-O), it is not particularly limited as long as it is a compound having a siloxane structure, and various silane coupling agents (coupling agents having a glycidyl group and / or an epoxycyclohexane group are essential). And a compound obtained by a sol-gel reaction with a component) and having a structure in which silicone oil or polyhydric alcohols are incorporated into the molecule as a segment.
Specific examples thereof include compounds described in republished patents WO2005 / 100445, Japanese Patent Application No. 2008-225472, and Japanese Patent Application Laid-Open No. 2007-326988.
These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be described.
Thermal curing with a curing agent (curable resin composition A)
The curable resin composition A of the present invention contains a curing agent having reactivity with the epoxy resin.
Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, etc. And their modified products, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Limited to is not. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydrides and carboxylic acid resins are particularly preferable.

  Examples of the compound having an acid anhydride structure include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2 , 1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride In particular, methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferable.

As the compound having a carboxylic acid structure (hereinafter referred to as polycarboxylic acid), a bi- to tetra-functional polycarboxylic acid is particularly preferable, and a 2- to 4-functional polyhydric alcohol is preferably added to an acid anhydride. The polycarboxylic acid obtained by this is preferable.
The 2- to 4-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol and norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, and tet such as pentaerythritol and ditrimethylolpropane Such as ols, and the like.
Particularly preferred alcohols are branched chains such as cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornene diol and the like. And cyclic alcohols.

  Examples of acid anhydrides for producing polycarboxylic acids include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [ 2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-Anhydrides are preferred.

  Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

  The acid anhydride and polycarboxylic acid can be used alone or in combination of two or more. In that case, the weight ratio of the acid anhydride to the polycarboxylic acid is 90/10 to 20/80, particularly preferably 80/20 to 30/70.

  In the curable resin composition A of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents in terms of functional group equivalent to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is 0.7-1.1 equivalent, Most preferably, it is 0.8-1.0 equivalent. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition A of the present invention, a curing catalyst can be used in combination with a curing agent, or a curing catalyst can be used alone without using a curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino- (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3, 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles, and imidazoles and phthalic acid, Isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4. 0) Diaza compounds such as undecene-7 and their Salts such as traphenylborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) ) Phosphines such as phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts, tin octylate, and the like, and Examples thereof include a microcapsule type curing accelerator obtained by making these curing accelerators into microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

  The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Contains phosphorus obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, binder resin can also be mix | blended with the curable resin composition A of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

  When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement mechanical strength without impairing the sex. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less.

When using the curable resin composition A of this invention for an optical material, especially an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y _{4 A l2 O 9: Ce,} Y 2 O 2 S: Eu, Sr 5 (PO 4) 3 Cl: Eu, (SrEu) such as _O · _Al 2 O ₃ is exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, 5-60 weight part is preferable.

  When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation during curing of various phosphors, silica fine powder (also called Aerosil or Aerosol) is used. An agent for imparting thixotropic properties can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The curable resin composition A of the present invention is an optical material, in particular, an optical semiconductor encapsulant contains an amine compound as a light stabilizer or a phosphorus compound or phenol compound as an antioxidant for the purpose of preventing coloring. can do.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2, 6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6, -tetramethyl -4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] buty Malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, N, N ′, N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2, 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and Polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3 , 20-diazadispiro [5.1.1.12] heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3 , 20-diazadispiro [5.1.1.12] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5.1.1.12]- Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2 , 2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl), etc. Hindered amine series, benzophenone series compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction product, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4- Benzoate type such as tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [ (Hexyl) oxy] triazine compounds such as phenol and the like can be mentioned, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA, LA-52, LA-57, LA-, manufactured by Ciba Specialty Chemicals. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)- , 4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3 '-Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite Bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di -N-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl Phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is below.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as a product made from ADEKA, Adeastab PEP-4C, Adeastab PEP-8, Adeastab PEP-24G, Adeastab PEP-36, Adeastab HP-10, Adeastab 2112, Adeastab 260 ADEASTAB 522A, ADEASTAB 1178, ADEASTAB 1500, ADEASTAB C, ADEASTAB 135A, ADEASTAB 3010, and ADEASTAB TPP.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butyl) Enol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), Bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert -Pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- ( 4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester, and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, Adekas 1520L AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL INDUSTRIES, SUMITIZER GA-80, SUMILIZER MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like are manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the above phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0.005 to 5 with respect to the curable resin composition. The range is 0.0% by weight.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent, if necessary, until uniform using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly to obtain a curable resin composition. If the curable resin composition is in liquid form, potting or casting, impregnating the substrate, pouring the curable resin composition into a mold, casting, and heating. In the case of curing or solid, there is a method of molding after melting or casting using a transfer molding machine or the like, and further curing by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed between 80 and 150 ° C., and post-curing is performed between 100 and 200 ° C. As the curing stage, the temperature is preferably divided into 2 to 8 stages, more preferably 2 to 4 stages.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a curable resin composition varnish, and glass fiber. A cured product of the curable resin composition of the present invention by hot press-molding a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. It can be. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

Moreover, the curable resin composition A of this invention can also be used as a film type sealing composition. When obtaining such a film-type resin composition, the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
Next, the case where the epoxy resin composition of the present invention is used as an optical semiconductor sealing material or die bonding material will be described in detail.

  When the curable resin composition A of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED or a die bond material, the curing agent (curing agent composition) containing the polyvalent carboxylic acid of the present invention. In addition to the epoxy resin, an epoxy resin composition is prepared by thoroughly mixing additives such as a curing accelerator, a coupling material, an antioxidant, a light stabilizer, etc., and as a sealing material or a die bond material Used for both encapsulants. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The curable resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

  As a method for adhering a semiconductor chip to a substrate using the curable resin composition A of the present invention, the epoxy resin composition of the present invention is applied by dispenser, potting, or screen printing, and then heated by placing the semiconductor chip thereon. Curing can be performed to bond the semiconductor chip. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.

  The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

Cationic curing with an acidic curing catalyst (curable resin composition B)
When the curable resin composition of the present invention is cured with an acidic curing catalyst, the curable resin composition of the present invention contains a photopolymerization initiator or a thermal polymerization initiator. Furthermore, the curable resin composition B may be prepared by using a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiation aid, a photosensitizer, an inorganic filler, a pigment, an ultraviolet absorber, an antioxidant, Various known compounds and materials such as stabilizers, silane coupling materials, release agents, and various thermosetting resins may be contained.

Furthermore, specific examples of the inorganic filler and the release agent that the curable resin composition B of the present invention contains as necessary include those similar to the curable resin composition A.
As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compound (US Pat. No. 3,708,296), aromatic onium salt of group VIa element (US Pat. No. 4,058,400), aromatic onium salt of group Va element (US Pat. No. 4069055), dicarbonyl chelate of group IIIa to Va element (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF ₆ -anions (US Pat. No. 4,161,478; M is selected from phosphorus, antimony and arsenic). Arylsulfonium complex salts (US Pat. No. 4,231,951), Aromatic iodonium and aromatic sulfonium complexes (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2, 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like.
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

  Furthermore, it is possible to simultaneously use one or two or more of these photocationic polymerization initiators, known polymerization initiation assistants and photosensitizers. Examples of polymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone di Chiruketaru, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone. The usage-amount of polymerization initiation adjuvants, such as photoradical polymerization initiator, is 0.01-30 weight part with respect to 100 weight part of components which can carry out photoradical, Preferably it is 0.1-10 weight part.

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of all the epoxy resin components, Preferably it is 0.1-10 weight part.

  Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins can be added to the curable resin composition B of the present invention as necessary. . Specific examples are as described above.

The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying.
The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable curable resin composition hardens | cures, and should just satisfy | fill the hardening conditions with which the adhesive strength of hardened | cured material is favorable. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are highly transparent. Moreover, it is difficult for these epoxy resin-based photocuring to be completely cured only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.

  The heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . The molding method varies depending on the applicable part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, or the like can be applied. Although it is mentioned, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

  For example, when used for a cation curable resist, first, the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is used as a copper-clad laminate, The composition of the present invention is applied to a film thickness of 5 to 160 μm on a substrate such as a ceramic substrate or a glass substrate by a method such as screen printing or spin coating to form a coating film. The coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern. Then, post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transportation equipment, lamp reflectors for automobiles, bare ring retainers, gear parts, corrosion-resistant coatings, switch parts, headlamps, engine internal parts, electrical components, various interior and exterior products, drive engines, brake oil tanks, automotive Rust-proof steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automotive lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, under-filling such as BGA, CSP and the like when mounting IC packages (including a reinforcing underfill) can be used.

  Other uses of the optical material include general uses in which the curable resin composition A or the curable resin composition B is used. For example, adhesives, paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including a printed circuit board, wire coating, etc.), sealants, additives to other resins, and the like. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analytical conditions in gas chromatography (hereinafter referred to as GC) were HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) for the separation column, and the column oven temperature was set to an initial temperature of 100 ° C. The temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes. Helium was used as a carrier gas. Furthermore, in the measurement of gel permeation chromatography (hereinafter referred to as GPC), it is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI, and the standard curve made by Shodex was used for the calibration curve.

Example 1
A flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube was purged with nitrogen while 251 parts of 3-cyclohexenecarboxylic acid, 174 parts of monoallyltrimethylolpropane (manufactured by perstorp), 200 parts of toluene, 4 parts of toluenesulfonic acid was added, and the reaction was carried out for 10 hours while dehydrating with a Dean-Stark tube under heating and refluxing conditions.
After completion of the reaction, after cooling, washing with 80 parts of a 10% by weight aqueous sodium hydroxide solution three times, and further washing with water at 100 parts / time until the wastewater becomes neutral, heating the toluene under reduced pressure with a rotary evaporator. By distilling off, the following formula (1)

で表される化合物を主成分とする二官能性オレフィン樹脂（Ａ−１）を３８６部得た。得られた二官能性オレフィン樹脂（Ａ−１）をガスクロマトグラフィーで測定した結果、≧９８％の純度で得られていることが確認できた。

386 parts of bifunctional olefin resin (A-1) which has as a main component the compound represented by these was obtained. As a result of measuring the obtained bifunctional olefin resin (A-1) by gas chromatography, it was confirmed that it was obtained with a purity of ≧ 98%.

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 15 parts of water, 1.9 parts of 12-tungstophosphoric acid, 1.0 part of sodium tungstate, 1.6 parts of disodium hydrogen phosphate while purging with nitrogen. Part, 5.4 parts trioctylmethylammonium acetate (manufactured by Lion Akzo, 50 wt% xylene solution, TOMAA), 180 parts toluene, 185 parts bifunctional olefin resin (A-1) obtained in Synthesis Example 1, The solution was heated to 50 ° C. After raising the temperature, 107 parts of 35% by weight hydrogen peroxide water were added over 45 minutes while stirring, and the mixture was stirred at 50 ° C. for 8 hours.
Then, after neutralizing with 30 wt% aqueous sodium hydroxide solution, 25 parts of 20 wt% aqueous sodium thiosulfate solution was added and stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CP1 made by Ajinomoto Fine Techno) and 20 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer, whereby 199 parts of a liquid epoxy resin (EP-1) at room temperature (yield 94%, conversion of raw materials) Rate> 98%). The epoxy equivalent of the obtained epoxy resin was 217 g / eq. The amount of residual quaternary ammonium salt was 100 ppm or less, and the residual tungsten was 0.1 ppm.
According to gas chromatography (GC), the obtained epoxy resin is a compound containing 94% by area of the component represented by the following formula (2), and has a partially allylated allyl group as a by-product. %, It was confirmed that the monoepoxy compound contained 1% by area (identification is GC-MS).
Formula (2)

From the above results, it became clear that the target bifunctional epoxy resin can be obtained with high selectivity and high yield by using the production method of the present invention.
In addition, since the epoxy resin obtained by the present invention has a plurality of epoxy groups or (meth) allyl groups, it is useful as a thermosetting, photocurable epoxy resin or an epoxy resin raw material in which a three-dimensional network is important. In addition, since it can be expected to react with maleimide and the like, it can be seen that it is useful as a cross-linking material that can cope with various curing systems.

Claims (2)

A method for producing an epoxy resin having a (meth) allyl group and an epoxy group,
(A) Step of obtaining an aqueous solution containing tungstic acid and / or salt thereof, phosphoric acid and / or salt thereof (B) Step of adding quaternary ammonium salt whose counter anion is carboxylate ion (C) Hydrogen peroxide Including a step of adding an aqueous solution, either before or after the steps (A) to (C),
(D) Epoxidation is performed via a step of adding a compound having a (meth) allyl group and a cyclohexenyl group, and the epoxy resin is at least one of a metal composite salt, activated carbon, a layered clay mineral, a metal oxide, and a phenol resin polymer. A method for producing an epoxy resin, which comprises purifying by contacting with a seed. Such phosphoric acid and / or salts thereof, the (A) pH in the aqueous solution of step is characterized by using an amount to be adjusted in the range of 6-8, the method of manufacturing the epoxy resin according to claim 1 .